Ethyl Acetate → 4beta-Ethyl-6alpha-hydroxyandrostan-3,17-dione

HRID 1182892Notes

Reaction equation

HRID 1182892 reaction equation
[CH2:1]([C@H:3]1[C@H:20]([OH:21])[CH2:19][CH2:18][C@@:17]2([CH3:22])[CH:4]1[C@@H:5]([OH:24])[CH2:6][C@@H:7]1[C@@H:16]2[CH2:15][CH2:14][C@@:12]2([CH3:13])[C@H:8]1[CH2:9][CH2:10][C@@H:11]2[OH:23])[CH3:2].C1C(=O)N(Br)C(=O)C1.CCOC(C)=O.[O-]S([O-])=O.[Na+].[Na+]>O1CCOCC1.O.N1C=CC=CC=1>[CH2:1]([C@H:3]1[C:20](=[O:21])[CH2:19][CH2:18][C@@:17]2([CH3:22])[CH:4]1[C@@H:5]([OH:24])[CH2:6][C@@H:7]1[C@@H:16]2[CH2:15][CH2:14][C@@:12]2([CH3:13])[C@H:8]1[CH2:9][CH2:10][C:11]2=[O:23])[CH3:2]

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 24437Sodium SulfiteHCID 67184N-bromobutanimideHCID 687790364beta-Ethylandrostan-3alpha,6alpha,17beta-triol

Product 1

HCID 687318194beta-Ethyl-6alpha-hydroxyandrostan-3,17-dioneYield 57.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 1049PyridineSolventHCID 312751,4-DioxaneSolvent

Procedure

To a stirred solution of 4β-ethylandrostan-3α,6α,17β-triol (Preparation 11, 237 mg) in dioxane (5.8 ml), water (1.08 ml), pyridine (0.1 ml) and NBS (249 mg) were added. After 72 h, EtOAc (70 ml), H2O (30 ml) and 10% Na2SO3 aqueous solution (24 ml) were added and the mixture was stirred for 10 min. The phases were separated and the aqueous phase was extracted with EtOAc. The combined organic extracts were washed with of 5% aqueous NaHCO3, brine, dried over MgSO4, filtered and evaporated to dryness. The crude product was purified by flash chromatography (SiO2, EtOAc/n-hexane 70/30) to give the title compound as a white solid (135 mg, 57%).

Workup

  1. customThe phases were separated
  2. extractionthe aqueous phase was extracted with EtOAc
  3. washThe combined organic extracts were washed with of 5% aqueous NaHCO3, brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. customevaporated to dryness
  7. customThe crude product was purified by flash chromatography (SiO2, EtOAc/n-hexane 70/30)

Sources & evidence

ORD record
ord-504bc999511d4d709eb81275e0f5ab63
Source dataset
uspto-grants-2014_03
Patent number
US08664210B2

Reaction notes

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